Penetration of electronic states from silicon substrate into silicon oxide

The depth profiling of O 1s energy loss in silicon oxide near the SiO₂/Si interface was performed using extremely small probing depth. As a result, the energy loss of O 1s photoelectrons with threshold energy of 3.5 eV was found. This value of 3.5 eV is much smaller than the SiO₂ bandgap of 9.0 eV, but quite close to direct interband transition at Γ point in energy band structure of silicon. This can be explained by considering the penetration of electronic states from silicon substrate into silicon oxide up to 0.6 nm from the interface. In addition, the penetrating depth is larger than the thickness of the compositional transition layer.     

A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface

Zirconium oxide (ZrO₂) is one of the leading candidates to replace silicon oxide (SiO₂) as the gate dielectric for future generation metal-oxide-semiconductor (MOS) based nanoelectronic devices. Experimental studies have shown that a 1–3 monolayer SiO₂ film between the high permittivity metal oxide and the substrate silicon is needed to minimize electrical degradation. This study uses density functional theory (DFT) to investigate the initial growth reactions of ZrO₂ on hydroxylated SiO₂ by atomic layer deposition (ALD). The reactants investigated in this study are zirconium tetrachloride (ZrCl₄) and water (H₂O). Exchange reaction mechanisms for the two reaction half-cycles were investigated. For the first half-reaction, reaction of gaseous ZrCl₄ with the hydroxylated SiO₂ surface was studied. Upon adsorption, ZrCl₄ forms a stable intermediate complex with the surface SiO₂–OH^* site, followed by formation of SiO₂–O–Zr–Cl^* surface sites and HCl. For the second half-reaction, reaction of H₂O on SiO₂–O–Zr–Cl^* surface sites was investigated. The reaction pathway is analogous to that of the first half-reaction; water first forms a stable intermediate complex followed by evolution of HCl through combination of a Cl atom from the surface site and an H atom from H₂O. The results reveal that the stable intermediate complexes formed in both half-reactions can lead to a slow film growth rate unless process parameters are adjusted to lower the stability of the complex. The energetics of the two half-reactions are similar to those of ZrO₂ ALD on ZrO₂ and as well as the energetics of ZrO₂ ALD on hydroxylated silicon. The energetics of the growth reactions with two surface hydroxyl sites are also described.     

硅—二氧化硅界面过渡区的XPS研究

本文报道了用X射线光电子能谱的角度效应研究硅-二氧化硅界面过渡区的结果。样品为(111)取向的硅单晶片上低温(700℃)氧化生成的超薄氧化膜,膜的厚度不大于50?。氧化膜与单晶衬底中Si_2p光电子谱峰之间的化学位移(δ)和强度比(I_0x/I_si)随光电子发射角(θ)的变化明显地偏离理想界面所预期的结果,表明在硅-二氧化硅的界面处存在化学比为SiO_x(0yO_4-y(0≤y≤4)型四面体。比较实验曲线与随机成键模型的计算结果,估计出过渡区的宽度不大于20?,小于Si_2p光电子在二氧化硅中的平均逃逸深度。对改变氧化时间结合Ar⁺刻蚀制得的氧化膜厚度不同的样品所作的测量,得到与角度实验相一致的结果。 关键词：     

Real-time monitoring of SiO2/Si(1 1 1) interlayer etching by Brewster-angle reflectometry

A transitory etching regime after SiO₂ dissolution and before bulk Si(1 1 1) etching in neutral NH₄F solutions was monitored by in situ Brewster-angle reflectometry (BAR). An observed intermediate increase of the BAR reflectance signal is attributed to a fast dissolution of a stressed/strained interlayer beneath the SiO₂/Si(1 1 1) interface. Similar effects were observed on thin thermal oxides (18.2 nm), grown on float zone silicon, as well as on ultra-thin native oxides (1.2 nm) on Czochralsky silicon. Native oxide covered samples showed an increased surface roughness in the course of interlayer dissolution while the surface is progressively covered with compounds of fluorinated silicon. The etch rate, determined by atomic force microscopy (AFM) and compared to the etch rate of bulk silicon, is increased by a factor of four. In the limit of extended etching, the known low etch rates for silicon in 40% NH₄F are observed. Structural and chemical properties of the interfacial layer were analyzed by synchrotron radiation photoelectron spectroscopy (SRPES) which confirmed the presence of Si^3+/4+ valence states throughout the interlayer and by near open-circuit potential (N-OCP) dark current measurements. As a result, oxide etch rates in NH₄F in the pH-range 7–8 as well as the silicon interlayer depth can be assessed by in situ BAR.     

Ozone oxidation of 4H-SiC and flat-band voltage stability of SiC MOS capacitors

We investigate the effect of ozone (O₃) oxidation of silicon carbide (SiC) on the flat-band voltage (V_fb) stability of SiC metal-oxide-semiconductor (MOS) capacitors. The SiC MOS capacitors are produced by O₃ oxidation, and their V_fb stability under frequency variation, temperature variation, and bias temperature stress are evaluated. Secondary ion mass spectroscopy (SIMS), atomic force microscopy (AFM), and x-ray photoelectron spectroscopy (XPS) indicate that O₃ oxidation can adjust the element distribution near SiC/SiO₂ interface, improve SiC/SiO₂ interface morphology, and inhibit the formation of near-interface defects, respectively. In addition, we elaborate the underlying mechanism through which O₃ oxidation improves the V_fb stability of SiC MOS capacitors by using the measurement results and O₃ oxidation kinetics.     

High and low thermal nitridation of SiO2 thin films

Thin thermal SiO₂ films on crystalline silicon substrate were nitrided at low ammonia pressures (10^-6P_NH310^-1 mbar) for times varying from 1 to 10 h, by means of two techniques. (i) Surface nitridation has been achieved by thermal activation at high temperature (HT), in the range 800–1100°C. (ii) A new process at low temperature (LT), was employed at T ≈ 30°C, under electron-beam irradiation; the nitridation-reaction rate depends on the electron energy (reaching a maximum within the energy range 1 to 2 keV), and on the electron flux. Conduction and electron trapping on the nitrided oxide films depends on the chemical compositions and on the amount of nitrogen incorporated into the bulk of the films and/or at the SiO₂-Si interface.     

Time-dependent response of interface states determined by using differential isothermal transient spectroscopy

A method based on the differential analysis of the isothermal transients is proposed to study the dynamical properties of the charging and discharging of interface states, and several possibilities of using this method are shown. The results obtained in SiO₂/Si and Si₃N₄/SiO₂/Si samples are in agreement with the existence of a spatial and energy distribution of interface states within the insulator. From the experimental data, the concentration of traps within the insulator at 35 Å is estimated to be 5×10⁹ cm^-2 eV^-1, with a tunneling cross section 10^-19 cm², at E_c-E ≈ 0.2 eV.     

Formation of silver colloids in silver ion-exchanged soda-lime glasses during annealing

The structural and compositional changes of the soda-lime glasses during the formation of the silver colloids were analyzed by the X-ray Photoelectron Spectroscopy (XPS) in order to examine the silver colloid formation mechanism. The in situ behavior of silver and SiO₂ networks on the surfaces of silver ion-exchanged soda-lime glasses during heating and cooling processes in ultra-high vaccum was monitored. The results showed that silver diffuses toward the surface, precipitates, and crystallizes during heating and the total silver surface concentration is slowly increased during cooling. The concentration changes of oxidized and neutral Ag, a new non-bridging oxygen species (NBO^*), and a new silicon species (Si[a]) were applied to deduce a disappropriation reaction mechanism of Ag⁺ on the surface during annealing. The SiO₂ network is modified at temperatures below 350°C to accommodate more silver on the surface and to balance the extra charge carried by the Ag⁺. That the SiO₂ network polymerizes during annealing was deduced from the results of the higher binding energies of Si2p and O1s after annealing. This observation suggests that the reduction of the Gibbs free energies and the relaxation of tensile stress result in the formation of the silver colloids under thermal annealing.     

Si–SiO2 interface formation in low-dose low-energy separation by implanted oxygen materials

The evolution of the Si–SiO₂ interface morphology of low-dose low-energy separation by implanted oxygen materials was investigated by transmission electron microscopy and atomic force microscopy. The Si–SiO₂ interface morphology and the RMS roughness are strongly affected by the implantation conditions and the annealing process. Three main types of the domains including round, square, and pyramid shapes with the step-terrace structure were observed on the buried SiO₂ surface. Round domains are observed in the early stage of the annealing process, while the square and pyramid domains are observed after the high temperature annealing. The mean RMS roughness decreases with increasing time and annealing temperature, while in the 1350 °C 4-h annealed samples, the mean RMS roughness decreases with either increasing the implantation dose or decreasing implantation energy. The scaling analysis shows that the Si–SiO₂ interfaces were found to be self-affine on the short length scales with a roughness exponent above 0.50. Qualitative mechanisms of Si–SiO₂ surface flattening are presented in terms of the variations of morphological features with the processing conditions.     

Ba10(PO4)4(SiO4)2∶Eu2+荧光体的光谱特性

采用高温固相法合成了荧光体Ba₁₀（PO₄）₄（SiO₄）₂：Ce³⁺和Ba₁₀（PO₄）₄（SiO₄）₂：Eu²⁺,研究了两种荧光体的光谱特性。结果表明,两者都呈现较强的宽带激发特征。根据同种基质中Eu²⁺和Ce³⁺两种离子光谱特征的相关性,通过测得的Ba₁₀（PO₄）₂（SiO₄）₂基质中Ce³⁺的光谱数据估算了Ba₁₀（PO₄）₂（SiO₄）₂：Eu²⁺中Eu²⁺的斯托克斯位移（ΔS）和激发能量,估算结果与Ba₁₀（PO₄）₂（SiO₄）₂：Eu²⁺样品的光谱分析结果十分吻合。Ba₁₀（PO₄）₂（SiO₄）₂：Eu²⁺可以同时被紫光和蓝光激发,发出偏白的绿光,可用作白光LED的荧光粉。     

UHV-MOCVD growth of TiO2 on SiOx/Si(1 1 1): Interfacial properties reflected in the Si 2p photoemission spectra

Metal–organic chemical vapour deposition growth of titanium oxide on moderately pre-oxidised Si(1 1 1) using the titanium(IV) isopropoxide precursor has been studied for two different growth modes, reaction-limited growth at 300 °C and flux-limited growth at 500 °C. The interfacial properties have been characterized by monitoring synchrotron radiation excited Si 2p photoemission spectra. The cross-linking from oxidised Si to bulk Si after TTIP exposure has been found to be very similar to that of SiO_x/Si(1 1 1). However, the results show that the additional oxidation of Si most probably causes a corrugation of the SiO_x/Si interface. Those conclusions are valid for both growth modes. A model is introduced in which the amorphous interface region is described as (TiO₂)_x(SiO₂)_y where x and y changes linearly and continuously over the interface. The model quantifies how (TiO₂)_x(SiO₂)_y mixing changes the relative intensities of the signals from silicon oxide and silicon. The method can be generalised and used for the analyses of other metal-oxides on silicon.     

FORMATION OF A BURIED LAYER OF ALUMINIUM NITRIDE BY HIGH DOSE N2+ IMPLANTATION INTO ALUMINIUM

Aluminium films with various thickness between 700 nm and 1μm were deposited on Si (100) substrates, and 400 keV N₂⁺ ions with doses ranging from 4.3×10¹⁷ to 1.8×10¹⁸ N/cm² were implanted into the alu-minium films on silicon, Rutherford Backscattering (RBS) and channeling, secondary ion mass spectroscopy (SIMS), Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and spreading resistance probes (SRP) were used to characterize the synthesized aluminium nitride. The experiments showed that when the implantation dose was higher than a critical dose N_c, a buried stoichiometric AlN layer with high resistance was formed, while no apparent AlN XRD peaks in the as-implanted samples were observed; however, there was a strong AlN(100) diffraction peak appearing after annealing at 500 ℃ for 1h. The computer program, Implantation of Reactive Ions into Silicon (IRIS), has been modified and used to simulate the formation of the buried AlN layer as N₂⁺ is implanted into aluminium. We find a good agreement between experimental measurements and IRIS simulation.     

电离辐射对部分耗尽绝缘体上硅器件低频噪声特性的影响

本文针对辐射前后部分耗尽结构绝缘体上硅(SOI)器件的电学特性与低频噪声特性开展试验研究. 受辐射诱生埋氧化层固定电荷与界面态的影响, 当辐射总剂量达到1 M rad(Si) (1 rad = 10^-2 Gy)条件下, SOI器件背栅阈值电压从44.72 V 减小至12.88 V、表面电子有效迁移率从473.7 cm²/V·s降低至419.8 cm²/V· s、亚阈斜率从2.47 V/dec增加至3.93 V/dec; 基于辐射前后亚阈斜率及阈值电压的变化, 可提取得到辐射诱生界面态与氧化层固定电荷密度分别为5.33×10¹¹ cm^{- 2}与2.36×10¹² cm^-2. 受辐射在埋氧化层-硅界面处诱生边界陷阱、氧化层固定电荷与界面态的影响, 辐射后埋氧化层-硅界面处电子被陷阱俘获/释放的行为加剧, 造成SOI 器件背栅平带电压噪声功率谱密度由7×10^{- 10} V²·Hz^-1增加至1.8×10^-9 V² ·Hz^-1; 基于载流子数随机涨落模型可提取得到辐射前后SOI器件埋氧化层界面附近缺陷态密度之和约为1.42×10¹⁷ cm^-3·eV^-1和3.66×10¹⁷ cm^-3·eV^-1. 考虑隧穿削弱因子、隧穿距离与时间常数之间关系, 本文计算得到辐射前后埋氧化层内陷阱电荷密度随空间分布的变化.     

A molecular dynamics simulation of ultrathin oxide films onsilicon: Growth by thermal O atoms and sputtering by 100 eV Ar+ ions

Molecular dynamics was applied to study the growth and sputtering of ultrathin oxide films on (100) Si surfaces. A multibody potential which stabilized the Si/SiO₂ interface was used for this purpose. Oxide growth by exposure to O atoms was found to follow Langmuir-type kinetics with unity initial sticking coefficient of O and saturation coverage of around four monolayers, in agreement with experimental data. Sputtering of an ultrathin oxide film on silicon by 100 eV Ar⁺ ions was simulated to study ion-assisted surface cleaning. Ion irradiation was found to promote restructuring of the surface into oxide islands, as observed experimentally. Island formation was accompanied with an increase in surface roughness. The evolution of the surface state with ion dose was predicted quantitatively     

γ射线作用下氧化铪基MOS结构总剂量效应研究

使用原子层淀积方法得到了7.8 nm厚度的HfO₂薄膜并通过直接溅射金属铝电极得到了Al/HfO₂/Si MOS电容结构,测量得到了HfO₂基MOS结构在60Co γ射线辐照前后的电容-电压特性,使用原子力显微镜得到了HfO₂薄膜在辐照前后的表面微观形貌,使用X射线光电子能谱方法测量得到了HfO₂薄膜在辐照前后的化学结构变化。研究发现,使用原子层淀积方法制备的HfO₂薄膜表面质量较高;γ射线辐照在HfO₂栅介质中产生了数量级为1012 cm-2的负的氧化层陷阱电荷;HfO₂薄膜符合化学计量比,介质内部主要的缺陷为氧空位且随着辐照剂量的增加而增加,说明辐照在介质中引入了陷阱从而导致MOS结构性能的退化。     

YVO_4∶Eu~(3+)@SiO_2核壳结构纳米复合材料的合成与表征

用沉淀法制备了尺寸约为8 nm的YVO4∶Eu3+纳米粒子,然后用反相微乳液法在YVO4∶Eu3+纳米粒子的表面包覆了一层Si O2壳。利用XRD、TEM、UV-Vis吸收光谱和光致发光光谱对合成的样品进行了表征。得到的复合物具有较好的核壳结构,通过改变硅酸四乙酯的用量可以改变Si O2壳的厚度。研究了Si O2壳对YVO4∶Eu3+发光性质的影响,结果表明:包覆和未包覆的样品在紫外光激发下都有Eu3+的特征发射;随着Si O2壳厚度的增加,发光强度和量子效率越来越低,Eu3+格位对称性越来越高。     

A new method to determine Si/SiO2 interface recombination parameters using a gate-controlled point-junction diode under illumination

A new method is presented to determine Si/SiO₂ interface recombination parameters. The device employed is constituted by a polysilicon-oxide-semiconductor capacitor with a microscale central junction (a gate-controlled point-junction diode). The excess minority carriers are photo-generated rather than being injected, which results in a one-dimensional current flow normal to the Si/SiO₂interface. The minority carrier quasi-Fermi level is probed at the Si/SiO₂ interface by means of the point junction. The one-dimensionality of the current flow and the exact knowledge of the minority carrier quasi-Fermi level permit an accurate measurement of the recombination rate. The method has been applied to characterize p-type 100 Si/SiO₂ interfaces with boron dopant concentrations ranging from 2.2×10¹⁵ to 2.0×10¹⁷ cm^-3. Data analysis has been performed using a numerical scheme to find a quasi-exact solution for the current recombining at the interface. It was found that the interface recombination parameters (trap density and capture cross-sections) depend only weakly on trap energy in a wide range around midgap. The cross-section for capturing electrons (σ_n) was found to greatly exceed (by a factor of 10² to 10³) the cross-section for capturing holes (σ_p).     

Evolution of step-terrace structure at Si–SiO2 interface in SIMOX substrate during annealing

The step-terrace structures at the interface between the Si layer and the buried SiO₂ layer of a Separation by IMplanted OXygen substrate has been observed by using atomic force microscopy (AFM) after removing the SiO₂ and Si layers. The time evolution of the Si–SiO₂ interface roughness during high-temperature annealing was analyzed by the scaling analysis of AFM data. The correlation length exhibited a nice correspondence to the size of square domain structures. Decreasing in the index of the length scale indicates that the growth mechanism changes as the annealing proceeds.     

快重离子辐照对非晶态SiO2薄膜光致发光谱的影响

用湿氧化法在单晶硅表面生长了非晶态SiO2薄膜,再用高能Pb和Xe离子对薄膜进行辐照,最后用荧光光谱分析了辐照参数(剂量、电子能损值)与发光特性改变的相关性.研究发现,快重离子辐照能显著影响薄膜的发光特性,进一步分析显示,辐照导致了SiO2薄膜内O-Si-O缺陷、缺氧缺陷和非桥式氧空位缺陷的产生,且缺氧缺陷和非桥式氧空...     

Laser assisted chemical vapour deposition of silicon oxide layers

This paper focuses on the deposition of silicon oxide thin films, using laser assisted CVD based on a CO₂ laser, and on the feasibility of the process for coating porous silicon samples. Scanning electron and atomic force microscopy were used to analyse the morphology and microstructure of the films, while structure and chemical composition were determined by Fourier transform infrared and Rutherford backscattering spectroscopy. Two-wavelength ellipsometry was used for thickness and refractive index evaluation. The photoluminescence of SiO₂/PS was measured and compared with that of uncoated samples.